γ-Induced single-step synthesis of ethylene glycol from methanol-formaldehyde solutions.

Autor: Novoselov, A. I., Silaev, M. M., Bugaenko, L. T.
Předmět:
Zdroj: Theoretical Foundations of Chemical Engineering; Aug2010, Vol. 44 Issue 4, p432-435, 4p, 2 Graphs
Abstrakt: A mechanism is developed for the initiated nonbranched-chain formation of ethylene glycol in methanol-formaldehyde solutions at formaldehyde concentrations of 0.1–3.1 mol dm−3 and temperatures of 373–473 K. At a formaldehyde concentration of 1.4 mol dm−3 and T = 473 K, the radiation-chemical yield of ethylene glycol is 139 molecules per 100 eV. The effective activation energy of ethylene glycol formation is 25 ± 3 kJ mol−1. The quasi-steady-state treatment of the reaction network suggested here led to a rate equation accounting for the nonmonotonic dependence of the ethylene glycol formation rate on the concentration of the free (unsolvated) form of dissolved formaldehyde. It is demonstrated that the peak in this dependence is due to the competition between methanol and CH2=O for reacting with the adduct radical HOCH2CH2O. [ABSTRACT FROM AUTHOR]
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